CN110437551A - A kind of self-repair type environment-protective rubber material and preparation method thereof - Google Patents

A kind of self-repair type environment-protective rubber material and preparation method thereof Download PDF

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CN110437551A
CN110437551A CN201910764771.0A CN201910764771A CN110437551A CN 110437551 A CN110437551 A CN 110437551A CN 201910764771 A CN201910764771 A CN 201910764771A CN 110437551 A CN110437551 A CN 110437551A
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rubber material
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filler
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CN110437551B (en
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蔡美英
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Guangdong Banggu Chemical Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4829—Polyethers containing at least three hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/61—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
    • C08L23/22—Copolymers of isobutene; Butyl rubber ; Homo- or copolymers of other iso-olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

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  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The present invention discloses a kind of self-repair type environment-protective rubber material and preparation method thereof, is related to selfreparing rubber materials.The self-repair type environment-protective rubber material ingredient includes butyl rubber matrix, selfreparing filler, toughening stretch-proof filler, vulcanization aid dispersion；Wherein, vulcanization aid dispersion is made of zinc oxide, bentonite, sodium carboxymethylcellulose, Vulcanization accelerator TMTD, expanded graphite.Elder generation's ball milling obtains vulcanization aid dispersion when preparation, then obtains rubber material by mixing, vulcanization.The preparation method is not necessarily to harsh conditions, and simple controllable, the rubber material finished product generated after vulcanization no longer needs to add other reparation systems and thermoplastic composition, can reach good repairing effect in air atmosphere.The rubber material tearing strength can achieve 26.5KN/m, and tensile strength can achieve 10.9MPa, and bounce impact elasticity can achieve 62%, and self-healing properties reach 74.6%.

Description

A kind of self-repair type environment-protective rubber material and preparation method thereof
Technical field
The present invention relates to selfreparing field of rubber technology, and in particular to a kind of self-repair type environment-protective rubber material and its preparation Method.
Background technique
Rubber product is in its processing and forming and subsequent use process, inevitably by hot, mechanical, chemical and ultraviolet The environmental stimulis effect such as light irradiation, to cause, material internal generates local damage or micro-crack, micro-crack extension are eventually led to Material breaks substantially reduce use value and safety.Therefore the self-reparing capability for studying rubber material, is always rubber materials Research hotspot.Selfreparing refers to material itself to a kind of ability of defect self judgment, control and recovery.Self-repair material can With self detection, and material is extended to significantly improve the safety of material by certain mechanism self-healing micro-damage Service life.
Dummy owner currently used for rubber will include the following categories: (one) amine-epoxy repairing type utilizes epoxy reparation Reagent and amine hardener crosslink curing reaction in cracks, and amine hardener is stored in capsule, doughnut, micro-vascular structures In, when capsule or fiber impaired under external force, release amine hardener reaches local route repair effect；(2) molecule is spread Type is auxiliary agent by addition thermoplastic material, is added in polymer, fills up crackle gap using the mobility of thermoplastic Reach repairing effect；(3) Intrinsical repeatedly utilizes the molecular structure in polymer material with reversible reaction to realize, Including reversible covalent bonding and reversible non-covalent bonding, most study is to react to be made between furans and maleimide at present Self-repair material.
The patent of publication No. CN109111604A discloses a kind of selfreparing rubber material, by rubber matrix, selfreparing bullet Property performed polymer, carbon black, zinc oxide, stearic acid, anti-aging agent, antioxidant, promotor, vulcanizing agent be kneaded, vulcanization obtain, can reach Good selfreparing effect, has huge market application prospect and good economic and social benefits.But it has been investigated that, still So have the following problems: 1) each ingredient of rubber material can not be good compatible, and toxicity is higher, and cannot achieve rubber repeatedly from It repairs, so that temperature tolerance, toughness and stretch-resistance cannot ensure, reduces the service life of rubber material；2) pass through mostly Addition inorganic filler improves the toughness and tensile strength of rubber matrix, and poor with rubber matrix associativity, even if improving Toughness and tensile strength, and reduce self-healing properties；3) in the vulcanization aid or thermoplastic composition added, contain high toxicity object Matter, is unable to satisfy that rubber material is environment-friendly and low-toxicity, requirement of large-scale industrial production；4) preparation method is often needed to add other and be repaired Complex system and thermoplastic composition, temperature, vacuum condition are harsh, it is more difficult to control, the rubber material finished product generated after vulcanization is in air Do not have good repairing effect under atmosphere.
Summary of the invention
In order to overcome above-mentioned technical problem, the purpose of the present invention is to provide a kind of self-repair type environment-protective rubber material and Preparation method.
The purpose of the present invention can be achieved through the following technical solutions:
The present invention provides a kind of self-repair type environment-protective rubber material, the ingredient including following parts by weight: butyl rubber matrix 80-100 parts, 22-30 parts of selfreparing filler, 15-26 parts of toughening stretch-proof filler, 6-13 parts of vulcanization aid dispersion；Wherein, sulphur Change auxiliary agent dispersion to be composed of the following components in parts by weight: 1-3 parts of zinc oxide, 4-6 parts of bentonite, sodium carboxymethylcellulose 0.2- 0.8 part, 0.6-1.2 parts of Vulcanization accelerator TMTD, 1.5-2.5 parts of expanded graphite；
The preparation method of the selfreparing filler the following steps are included:
1) polyether polyol 330N is mixed with double amino-terminated linear polydimethylsiloxane-s according to mass ratio 1:0.9-1.1 After closing uniformly, 100-110 DEG C of vacuum defoamation handles to obtain mixed liquor a；Wherein, the hydroxyl value of polyether polyol 330N is 55-58mg KOH/g, acid value≤0.15mg KOH/g, moisture content≤0.1%；The viscosity of double amino-terminated linear polydimethylsiloxane-s is 4500-4600mPa·s；
2) isophorone diisocyanate and dibutyl tin dilaurate are added into mixed liquor a, is warming up to 65-75 DEG C simultaneously 20-30min is stirred, then is warming up to 100-110 DEG C of reaction 2-3h, stands to room temperature and obtains performed polymer；Wherein, isophorone two is different The additive amount of cyanate is the 5%-10% of polyether polyol 330N mass, and the additive amount of dibutyl tin dilaurate is that polyethers is more The 0.5-3% of first alcohol 330N mass；
3) performed polymer is dissolved in acetone and obtains prepolymer solution, use 3, the 3'- dihydroxy two of acetone solution in advance Diphenyl disulfide ether is slowly dropped in prepolymer solution, and after being added dropwise, 40-50 DEG C of stirring 40-60min pours into polytetrafluoroethylene (PTFE) In mold, 60-70 DEG C of vacuum, which is crosslinked 12-16 hours, obtains selfreparing filler.
Self-repair type environment-protective rubber material of the present invention, it is contemplated that existing amine-epoxy repairing type and molecule diffused rubber Reparation system, it is desirable that the amine hardener or thermoplastic released has good compatibility and heat-resisting quantity, it is also necessary to rubber Glue is processed after the processes such as mixing, mill, high temperature vulcanized, and good heat-resisting quantity, toughness, stretch-resistance are kept, so that plus Working hour requires harshness, increases raw material and processing cost.
Inventor has carried out a large amount of research and screening to the ingredient of the self-repair type environment-protective rubber material, by by polyethers Polyalcohol 330N is mixed with double amino-terminated linear polydimethylsiloxane-s, adds isophorone diisocyanate and two laurels Sour dibutyl tin, ester exchange reaction obtain dimethyl silicone polymer soft segment graft modification polyether polyurethane performed polymer.The pre-polymerization Body is dissolved in acetone solvent, and under the action of 3,3'- dihydroxy diphenyl disulfide, performed polymer is carried out very in the form of cystine linkage Sky crosslinking, obtains selfreparing filler.By the selfreparing filler and butyl rubber matrix be kneaded it is compound after, polyethers is birdsed of the same feather flock together ammonia The long-chain molecule of ester is uniformly distributed in rubber matrix, is wound from molecule angle, can be with toughening stretch-proof filler, vulcanization Auxiliary agent dispersion is well compatible.After rubber material is cracked, since dimethyl silicone polymer soft segment graft modification polyethers is birdsed of the same feather flock together The selfreparing filler that urethane performed polymer is formed is repaired containing there are many hydrogen bond, a variety of interaction of hydrogen bond are reset on siloxanes, urethane The crack of micro-meter scale further bridges crack gap, realizes the multiple selfreparing of rubber, and keep the good temperature tolerance of rubber, Toughness and stretch-resistance, to effectively extend the service life of the rubber material.
As a further solution of the present invention, the toughening stretch-proof filler the preparation method is as follows: by graphene oxide It is uniformly mixed with mother-of-pearl dispersion liquid according to mass ratio 1:6-8,100-200W ultrasonic vibration 10-20min obtains dispersion, adds Enter Tris buffer solution and dispersion pH value be adjusted to 8.5, be filtered by vacuum after pouring into mold, 105-110 DEG C vacuum drying at Solid-like is ground into the powdered of partial size 1-2mm.
Toughening stretch-proof filler of the invention, choosing graphene oxide and pearl dispersion liquid is raw material, by ultrasonic vibration, Adjusting pH, vacuum filtration, vacuum drying, crushing obtain.Since the surface of graphene oxide and edge contain carboxyl, hydroxyl, ring A variety of oxygen-containing groups such as oxygroup, carbonyl, are easy and other materials is with Covalent bonding together.Mother-of-pearl generally by 95% brittleness aragonite Piece and 5% organic matter (predominantly β-chitin and fibroin) alternately construct, and the stratiform for forming similar modern architecture is orderly " brick-mud " structure, the multilevel structure of this complexity, which makes mother-of-pearl not only, to be had high-intensitive but also has high tenacity.Disperse in mother-of-pearl In liquid, with mother-of-pearl covalent cross-linking can occur for a part of oxygen-containing group on graphene oxide, make the spacing of graphene sheet layer Increase, the compound of mother-of-pearl, so that the filler being prepared is rich in oxygen groups, can hold well into graphene oxide interlayer Easily in conjunction with rubber matrix, the tensile strength, toughness, elasticity modulus of rubber matrix are further increased.
As a further solution of the present invention, the mother-of-pearl dispersion liquid the preparation method is as follows: choose pearl shell, cut It goes after the impurity of surface layer to use the salt acid soak 5-10min of 20vt%, reuses clear water flushing, precomminution is grown up 1-2cm, width 1- The tablet of 2cm is put into ball mill, and ball milling 2-3h obtains ball milling material under 35-45 DEG C, 300-400r/min, and ball milling material is added 10-12 times of quality of deionized water, ultrasonic vibration 10-20min at 40-50 DEG C.
The preparation method of mother-of-pearl dispersion liquid of the invention, including pearl shell remove skim-coat impurity, salt acid soak, pre- powder Broken, ball milling, deionized water mixing, ultrasonic vibration.Deposition calcium carbonate and the microorganism on surface etc. can be removed by cutting surface layer impurity Impurity, improves the mother-of-pearl content in clam shell, and salt acid soak can kill microorganism remained on surface and hydrolyze the carbonic acid on surface layer Calcium further increases mother-of-pearl content, by increasing the specific surface area of clam shell after precomminution, by grinding for ball mill Afterwards, the high-content mother-of-pearl of uniform particle sizes, stable structure, ultrasonic vibration after mother-of-pearl is mixed with deionized water, ultrasound are obtained Acoustic pressure drastic change when wave is propagated in deionized water makes system that strong cavitation and emulsion occur, and generates millions of each second The small cavitation bubble of meter, bubble is hastily a large amount of under acoustic pressure effect to be generated, and constantly fierce explosion, generates powerful rush Power and negative-pressure sucking are hit, so that the dirt on mother-of-pearl is sufficiently removed, and sufficiently kills bacterium, virus, is convenient for subsequent mother-of-pearl The cross-linking reaction of dispersion liquid and graphene oxide.
As a further solution of the present invention, the graphene oxide the preparation method is as follows: being sequentially added into beaker 1.2g expanded graphite, 20mL water, the hydrogen peroxide of 5mL volumetric concentration 27.5%, 0.5g oxalic acid, are mixing uniformly to form slurry, mix The slurry got togather is sprayed by booster pump with Sprayable in 215-225 DEG C of gasification burner, and slurry gasifies to form gas and pass through Tube-cooled absorbs, and isolates solid powder, filters, and washing is dried to obtain；Wherein, the density of expanded graphite is 1.92- 1.95g/cm3, crystal particle diameter is 50-60 mesh, and scale is having a size of 280-300 μm.
Graphene oxide preparation method of the invention, it is contemplated that existing method is carried out using toxic strong acid and strong oxidizer Oxidation reaction obtains, although imparting the good surface-active of graphene and compatibility, the waste liquid generated seriously pollutes ring Border requires further improvement.The present invention chooses expanded graphite as raw material, and hydrogen peroxide is as oxidant, and oxalic acid is as acid point Dispersion liquid, due to the good flexibility of expanded graphite, resilience, plasticity, booster pump pressurization is sprayed into high-temperature gasification furnace, promotes object The fast decoupled of matter, gasification, so that graphite flake layer separation, efficiently prepares graphene oxide.The graphene preparation method, raw material ring Low toxicity is protected, post-processing is simple, is suitble to industrialized production.
The present invention also provides the preparation methods of above-mentioned self-repair type environment-protective rubber material, comprising the following steps:
S1,1-3 parts of zinc oxide, 4-6 parts of bentonite, 0.2-0.8 parts of sodium carboxymethylcellulose, Vulcanization accelerator TMTD are weighed 0.6-1.2 parts, 1.5-2.5 parts of expanded graphite obtain mixture after mixing, and mixture is added in ball mill, at 40-50 DEG C Under with revolving speed ball milling 2-3 hours of 350-400r/min obtain vulcanization aid dispersion；
S2, butyl rubber matrix, selfreparing filler, toughening stretch-proof filler are put into rubber mixing mill, mixing 20- 30min is poured into Teflon mould, and 90-100 DEG C obtains rubber semi-finished product in vacuumize process 1-2 hours；
S3, vulcanization aid dispersion is added in rubber semi-finished product, 120-130 DEG C of vulcanization 20-30min obtains this and review one's lessons by oneself Replica environment-protective rubber material.
The preparation method of self-repair type environment-protective rubber material of the present invention, compared with existing preparation method, first by butyl rubber It is kneaded in matrix body and, selfreparing filler, toughening stretch-proof filler investment rubber mixing mill, then carries out vacuumize process and obtain half Finished product, then mix vulcanization with vulcanization aid dispersion and obtain finished product.On the one hand, the swelling soil loosening in vulcanization aid dispersion is more Hole, adhesiveness are good；The good flexibility of expanded graphite, resilience, plasticity；Sodium carboxymethylcellulose, bentonite and expansion stone After ink combines, absorption package is carried out to Vulcanization accelerator TMTD, zinc oxide under the smashing and grinding effect of ball mill, so that the vulcanization aid Good resilience, plasticity, dispersibility is presented in dispersion, being capable of slow release Vulcanization accelerator TMTD, promotion in sulfidation The uniform and stable vulcanization of rubber semi-finished product.The preparation method is not necessarily to harsh conditions, simple controllable, the rubber material generated after vulcanization Finished product no longer needs to add other reparation systems and thermoplastic composition, can reach good repairing effect in air atmosphere, be in Existing good toughness, stretch-resistance and heat-resisting quantity.
Beneficial effects of the present invention:
1, self-repair type environment-protective rubber material of the present invention, by by polyether polyol 330N and double amino-terminated linear poly- two Methylsiloxane mixing, adds isophorone diisocyanate and dibutyl tin dilaurate, ester exchange reaction obtains poly- two Methylsiloxane soft segment graft modification polyether polyurethane performed polymer.The performed polymer is dissolved in acetone solvent, in 3,3'- dihydroxy Under the action of base diphenyl disulfide, performed polymer carries out vacuum crosslinking in the form of cystine linkage, obtains selfreparing filler；The selfreparing Filler is wound from molecule angle, can be well compatible with toughening stretch-proof filler, vulcanization aid dispersion；Rubber material goes out After existing crackle, due to the selfreparing filler that dimethyl silicone polymer soft segment graft modification polyether polyurethane performed polymer is formed, silicon Containing there are many hydrogen bond on oxygen alkane, urethane, a variety of interaction of hydrogen bond reset the crack for repairing micro-meter scale, further bridge crack Gap realizes the multiple selfreparing of rubber, and keeps the good temperature tolerance of rubber, toughness and stretch-resistance, so that effectively extending should The service life of rubber material.
2, carboxyl, hydroxyl, epoxy are contained in toughening stretch-proof filler of the invention, the surface and edge of ingredient graphene oxide A variety of oxygen-containing groups such as base, carbonyl, are easy and other materials is with Covalent bonding together；A part of oxygen-containing group on graphene oxide Covalent cross-linking can occur with mother-of-pearl, increase the spacing of graphene sheet layer, the compound of mother-of-pearl can be well into oxygen Graphite alkene interlayer is easy in conjunction with rubber matrix so that the filler being prepared is rich in oxygen groups, further increases rubber-based The tensile strength of body, toughness, elasticity modulus.
3, the preparation method of mother-of-pearl dispersion liquid of the invention, compared with the conventional method, by grinding for ball mill Afterwards, the high-content mother-of-pearl of uniform particle sizes, stable structure, ultrasonic vibration after mother-of-pearl is mixed with deionized water, ultrasound are obtained Acoustic pressure drastic change when wave is propagated in deionized water makes system that strong cavitation and emulsion occur, and generates millions of each second The small cavitation bubble of meter, bubble is hastily a large amount of under acoustic pressure effect to be generated, and constantly fierce explosion, generates powerful rush Power and negative-pressure sucking are hit, so that the dirt on mother-of-pearl is sufficiently removed, and sufficiently kills bacterium, virus, is convenient for subsequent mother-of-pearl The cross-linking reaction of dispersion liquid and graphene oxide.
4, graphene oxide preparation method of the invention chooses expanded graphite as raw material, dioxygen compared with the conventional method Water is as oxidant, and oxalic acid is as acid dispersion, due to the good flexibility of expanded graphite, resilience, plasticity, booster pump Pressurization sprays into high-temperature gasification furnace, promotes fast decoupled, the gasification of substance, so that graphite flake layer separates, efficient preparation oxidation stone Black alkene.Compared with the conventional method, raw material is environment-friendly and low-toxicity for the graphene preparation method, and post-processing is simple, is suitble to industrialized production.
5, the preparation method of self-repair type environment-protective rubber material of the present invention, compared with existing preparation method, carboxymethyl is fine After plain sodium, bentonite are tieed up in conjunction with expanded graphite, Vulcanization accelerator TMTD, zinc oxide are inhaled under the smashing and grinding effect of ball mill Attached package can delay so that good resilience, plasticity, dispersibility is presented in the vulcanization aid dispersion in sulfidation On The Drug Release Vulcanization accelerator TMTD, the vulcanization for promoting rubber semi-finished product uniform and stable.The preparation method is not necessarily to harsh conditions, simply may be used Control, the rubber material finished product generated after vulcanization no longer need to add other reparation systems and thermoplastic composition, can be in air atmosphere Under reach good repairing effect.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical scheme in the embodiment of the invention is clearly and completely described, Obviously, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based in the present invention Embodiment, all other embodiment obtained by those of ordinary skill in the art without making creative efforts, all Belong to the scope of protection of the invention.
Embodiment 1
The present embodiment provides a kind of self-repair type environment-protective rubber material, the ingredient including following parts by weight: butyl rubber base 92 parts of body, 26 parts of selfreparing filler, 20 parts of toughening stretch-proof filler, 9 parts of vulcanization aid dispersion.
Vulcanization aid dispersion is composed of the following components in parts by weight: 1.6 parts of zinc oxide, 5.2 parts of bentonite, carboxymethyl are fine Tie up plain 0.4 part of sodium, 0.9 part of Vulcanization accelerator TMTD, 2.3 parts of expanded graphite.
Wherein selfreparing filler preparation method the following steps are included:
1) polyether polyol 330N is uniformly mixed with double amino-terminated linear polydimethylsiloxane-s according to mass ratio 1:1 Afterwards, 106 DEG C of vacuum defoamations handle to obtain mixed liquor a；Wherein, the hydroxyl value of polyether polyol 330N is 55-58mg KOH/g, acid value ≤ 0.15mg KOH/g, moisture content≤0.1%；The viscosity of double amino-terminated linear polydimethylsiloxane-s is 4500-4600mPa s；
2) isophorone diisocyanate and dibutyl tin dilaurate are added into mixed liquor a, is warming up to 69 DEG C and stirs 28min is mixed, then is warming up to 108 DEG C of reaction 2.5h, stands to room temperature and obtains performed polymer；Wherein, isophorone diisocyanate Additive amount is the 6% of polyether polyol 330N mass, and the additive amount of dibutyl tin dilaurate is polyether polyol 330N mass 1%；
3) performed polymer is dissolved in acetone and obtains prepolymer solution, use 3, the 3'- dihydroxy two of acetone solution in advance Diphenyl disulfide ether is slowly dropped in prepolymer solution, and after being added dropwise, 48 DEG C of stirring 50min are poured into Teflon mould, 68 DEG C of vacuum, which are crosslinked 14 hours, obtains selfreparing filler.
Toughening stretch-proof filler the preparation method is as follows: by graphene oxide and mother-of-pearl dispersion liquid according to mass ratio 1: 7.5 are uniformly mixed, and 150W ultrasonic vibration 16min obtains dispersion, and Tris buffer solution is added and adjusts dispersion pH value To 8.5, it is filtered by vacuum after pouring into mold, 108 DEG C of vacuum drying are ground into the powdered of partial size 1-2mm at solid-like.
Mother-of-pearl dispersion liquid the preparation method is as follows: choose pearl shell, cut the salt that 20vt% is used after the impurity of surface layer Acid soak 8min, reuses clear water flushing, and the tablet of precomminution growth 1-2cm, width 1-2cm are put into ball mill, in 40 DEG C, ball milling 2.5h obtains ball milling material under 360r/min, the deionized water of 11 times of ball milling material quality, ultrasonic vibration at 46 DEG C is added 18min.
Graphene oxide the preparation method is as follows: sequentially adding 1.2g expanded graphite, 20mL water, 5mL volume into beaker Hydrogen peroxide, the 0.5g oxalic acid of concentration 27.5%, are mixing uniformly to form slurry, and the slurry mixed is by booster pump with spraying shape Formula sprays into 220 DEG C of gasification burner, and slurry gasifies to form gas and absorb by tube-cooled, isolates solid powder, filters, Washing, is dried to obtain；Wherein, the density of expanded graphite is 1.92-1.95g/cm3, crystal particle diameter is 50-60 mesh, scale size It is 280-300 μm.
The preparation method of the present embodiment self-repair type environment-protective rubber material, comprising the following steps:
S1, zinc oxide, bentonite, sodium carboxymethylcellulose, Vulcanization accelerator TMTD, expanded graphite are weighed, after mixing To mixture, mixture is added in ball mill, obtains vulcanization aid point at 48 DEG C with the revolving speed ball milling of 370r/min 2.8 hours Granular media；
S2, butyl rubber matrix, selfreparing filler, toughening stretch-proof filler are put into rubber mixing mill, mixing 25min is poured into Teflon mould, and 96 DEG C obtain rubber semi-finished product in vacuumize process 1.8 hours；
S3, vulcanization aid dispersion is added in rubber semi-finished product, 127 DEG C of vulcanization 30min, obtains self-repair type environmental protection Rubber material.
Embodiment 2
The present embodiment provides a kind of self-repair type environment-protective rubber material, the ingredient including following parts by weight: butyl rubber base 95 parts of body, 27 parts of selfreparing filler, 23 parts of toughening stretch-proof filler, 10 parts of vulcanization aid dispersion.
Vulcanization aid dispersion is composed of the following components in parts by weight: 2.2 parts of zinc oxide, 5.6 parts of bentonite, carboxymethyl are fine Tie up plain 0.6 part of sodium, 1.1 parts of Vulcanization accelerator TMTD, 2.1 parts of expanded graphite.
Wherein selfreparing filler preparation method the following steps are included:
1) polyether polyol 330N is mixed with double amino-terminated linear polydimethylsiloxane-s according to mass ratio 1:0.96 After uniformly, 107 DEG C of vacuum defoamations handle to obtain mixed liquor a；Wherein, the hydroxyl value of polyether polyol 330N is 55-58mg KOH/g, Acid value≤0.15mg KOH/g, moisture content≤0.1%；The viscosity of double amino-terminated linear polydimethylsiloxane-s is 4500- 4600mPa·s；
2) isophorone diisocyanate and dibutyl tin dilaurate are added into mixed liquor a, is warming up to 73 DEG C and stirs 27min is mixed, then is warming up to 102 DEG C of reaction 2.8h, stands to room temperature and obtains performed polymer；Wherein, isophorone diisocyanate Additive amount is the 7% of polyether polyol 330N mass, and the additive amount of dibutyl tin dilaurate is polyether polyol 330N mass 1.6%；
3) performed polymer is dissolved in acetone and obtains prepolymer solution, use 3, the 3'- dihydroxy two of acetone solution in advance Diphenyl disulfide ether is slowly dropped in prepolymer solution, and after being added dropwise, 48 DEG C of stirring 55min are poured into Teflon mould, 70 DEG C of vacuum, which are crosslinked 15 hours, obtains selfreparing filler.
Toughening stretch-proof filler the preparation method is as follows: by graphene oxide and mother-of-pearl dispersion liquid according to mass ratio 1: 7.5 are uniformly mixed, and 160W ultrasonic vibration 18min obtains dispersion, and Tris buffer solution is added and adjusts dispersion pH value To 8.5, it is filtered by vacuum after pouring into mold, 110 DEG C of vacuum drying are ground into the powdered of partial size 1-2mm at solid-like.
Mother-of-pearl dispersion liquid the preparation method is as follows: choose pearl shell, cut the salt that 20vt% is used after the impurity of surface layer Acid soak 9min, reuses clear water flushing, and the tablet of precomminution growth 1-2cm, width 1-2cm are put into ball mill, in 42 DEG C, ball milling 2.8h obtains ball milling material under 400r/min, the deionized water of 11 times of ball milling material quality, ultrasonic vibration at 48 DEG C is added 18min.
The preparation method of graphene oxide is same as Example 1.
The preparation method of the present embodiment self-repair type environment-protective rubber material, comprising the following steps:
S1, zinc oxide, bentonite, sodium carboxymethylcellulose, Vulcanization accelerator TMTD, expanded graphite are weighed, after mixing To mixture, mixture is added in ball mill, obtains vulcanization aid dispersion at 50 DEG C with the revolving speed ball milling of 380r/min 3 hours Body；
S2, butyl rubber matrix, selfreparing filler, toughening stretch-proof filler are put into rubber mixing mill, mixing 26min is poured into Teflon mould, and 98 DEG C obtain rubber semi-finished product in vacuumize process 2 hours；
S3, vulcanization aid dispersion is added in rubber semi-finished product, 130 DEG C of vulcanization 23min, obtains self-repair type environmental protection Rubber material.
Embodiment 3
The present embodiment provides a kind of self-repair type environment-protective rubber material, the ingredient including following parts by weight: butyl rubber base 92 parts of body, 25 parts of selfreparing filler, 24 parts of toughening stretch-proof filler, 10 parts of vulcanization aid dispersion.
Vulcanization aid dispersion is composed of the following components in parts by weight: 2.6 parts of zinc oxide, 5.6 parts of bentonite, carboxymethyl are fine Tie up plain 0.7 part of sodium, 1.1 parts of Vulcanization accelerator TMTD, 2.3 parts of expanded graphite.
Wherein selfreparing filler preparation method the following steps are included:
1) polyether polyol 330N is mixed with double amino-terminated linear polydimethylsiloxane-s according to mass ratio 1:1.06 After uniformly, 106 DEG C of vacuum defoamations handle to obtain mixed liquor a；Wherein, the hydroxyl value of polyether polyol 330N is 55-58mg KOH/g, Acid value≤0.15mg KOH/g, moisture content≤0.1%；The viscosity of double amino-terminated linear polydimethylsiloxane-s is 4500- 4600mPa·s；
2) isophorone diisocyanate and dibutyl tin dilaurate are added into mixed liquor a, is warming up to 73 DEG C and stirs 26min is mixed, then is warming up to 108 DEG C of reaction 2.8h, stands to room temperature and obtains performed polymer；Wherein, isophorone diisocyanate Additive amount is the 6% of polyether polyol 330N mass, and the additive amount of dibutyl tin dilaurate is polyether polyol 330N mass 2.2%；
3) performed polymer is dissolved in acetone and obtains prepolymer solution, use 3, the 3'- dihydroxy two of acetone solution in advance Diphenyl disulfide ether is slowly dropped in prepolymer solution, and after being added dropwise, 50 DEG C of stirring 50min are poured into Teflon mould, 68 DEG C of vacuum, which are crosslinked 15 hours, obtains selfreparing filler.
Toughening stretch-proof filler the preparation method is as follows: by graphene oxide and mother-of-pearl dispersion liquid according to mass ratio 1:8 It is uniformly mixed, 190W ultrasonic vibration 18min obtains dispersion, and Tris buffer solution is added and is adjusted to dispersion pH value 8.5, it is filtered by vacuum after pouring into mold, 110 DEG C of vacuum drying are ground into the powdered of partial size 1-2mm at solid-like.
Mother-of-pearl dispersion liquid the preparation method is as follows: choose pearl shell, cut the salt that 20vt% is used after the impurity of surface layer Acid soak 9min, reuses clear water flushing, and the tablet of precomminution growth 1-2cm, width 1-2cm are put into ball mill, in 45 DEG C, ball milling 3h obtains ball milling material under 400r/min, the deionized water of 12 times of ball milling material quality, ultrasonic vibration 16min at 48 DEG C is added .
The preparation method of graphene oxide is same as Example 1.
The preparation method of the present embodiment self-repair type environment-protective rubber material, comprising the following steps:
S1, zinc oxide, bentonite, sodium carboxymethylcellulose, Vulcanization accelerator TMTD, expanded graphite are weighed, after mixing To mixture, mixture is added in ball mill, obtains vulcanization aid dispersion at 47 DEG C with the revolving speed ball milling of 400r/min 3 hours Body；
S2, butyl rubber matrix, selfreparing filler, toughening stretch-proof filler are put into rubber mixing mill, mixing 28min is poured into Teflon mould, and 97 DEG C obtain rubber semi-finished product in vacuumize process 1.8 hours；
S3, vulcanization aid dispersion is added in rubber semi-finished product, 128 DEG C of vulcanization 26min, obtains self-repair type environmental protection Rubber material.
Embodiment 4
The present embodiment provides a kind of self-repair type environment-protective rubber material, the ingredient including following parts by weight: butyl rubber base 100 parts of body, 28 parts of selfreparing filler, 25 parts of toughening stretch-proof filler, 12 parts of vulcanization aid dispersion.
Vulcanization aid dispersion is composed of the following components in parts by weight: 2.6 parts of zinc oxide, 5.5 parts of bentonite, carboxymethyl are fine Tie up plain 0.7 part of sodium, 1.1 parts of Vulcanization accelerator TMTD, 2.5 parts of expanded graphite.
Wherein selfreparing filler preparation method the following steps are included:
1) polyether polyol 330N is mixed with double amino-terminated linear polydimethylsiloxane-s according to mass ratio 1:1.1 After even, 108 DEG C of vacuum defoamations handle to obtain mixed liquor a；Wherein, the hydroxyl value of polyether polyol 330N is 55-58mg KOH/g, acid Value≤0.15mg KOH/g, moisture content≤0.1%；The viscosity of double amino-terminated linear polydimethylsiloxane-s is 4500- 4600mPa·s；
2) isophorone diisocyanate and dibutyl tin dilaurate are added into mixed liquor a, is warming up to 75 DEG C and stirs 28min is mixed, then heats up 110 DEG C and reacts 2h, stands to room temperature and obtains performed polymer；Wherein, the addition of isophorone diisocyanate Amount is the 8% of polyether polyol 330N mass, and the additive amount of dibutyl tin dilaurate is polyether polyol 330N mass 2%；
3) performed polymer is dissolved in acetone and obtains prepolymer solution, use 3, the 3'- dihydroxy two of acetone solution in advance Diphenyl disulfide ether is slowly dropped in prepolymer solution, and after being added dropwise, 50 DEG C of stirring 56min are poured into Teflon mould, 70 DEG C of vacuum, which are crosslinked 16 hours, obtains selfreparing filler.
Toughening stretch-proof filler the preparation method is as follows: by graphene oxide and mother-of-pearl dispersion liquid according to mass ratio 1:6- 8 are uniformly mixed, and 100-200W ultrasonic vibration 10-20min obtains dispersion, and Tris buffer solution is added by dispersion pH value 8.5 are adjusted to, is filtered by vacuum after pouring into mold, 105-110 DEG C of vacuum drying is ground into the powder of partial size 1-2mm at solid-like Shape.
Mother-of-pearl dispersion liquid the preparation method is as follows: choose pearl shell, cut the salt that 20vt% is used after the impurity of surface layer Acid soak 10min, reuses clear water flushing, and the tablet of precomminution growth 1-2cm, width 1-2cm are put into ball mill, in 45 DEG C, ball milling 2.2h obtains ball milling material under 400r/min, the deionized water of 12 times of ball milling material quality, ultrasonic vibration at 50 DEG C is added 15min.
The preparation method of graphene oxide is same as Example 1.
The preparation method of the present embodiment self-repair type environment-protective rubber material, comprising the following steps:
S1, zinc oxide, bentonite, sodium carboxymethylcellulose, Vulcanization accelerator TMTD, expanded graphite are weighed, after mixing To mixture, mixture is added in ball mill, obtains vulcanization aid point at 50 DEG C with the revolving speed ball milling of 390r/min 2.5 hours Granular media；
S2, butyl rubber matrix, selfreparing filler, toughening stretch-proof filler are put into rubber mixing mill, mixing 30min is poured into Teflon mould, and 100 DEG C obtain rubber semi-finished product in vacuumize process 1.6 hours；
S3, vulcanization aid dispersion is added in rubber semi-finished product, 130 DEG C of vulcanization 28min, obtains self-repair type environmental protection Rubber material.
Comparative example 1
This comparative example the difference from embodiment 1 is that, selfreparing filler using publication No. CN109111604A patent in Selfreparing elastomeric prepolymer body prepared by embodiment 1.
Comparative example 2
This comparative example the difference from embodiment 1 is that, toughening stretch-proof filler use nano silica.
Comparative example 3
This comparative example the difference from embodiment 1 is that, vulcanization aid dispersion replaces with Vulcanization accelerator TMTD.
Comparative example 4
This comparative example the difference from embodiment 1 is that, by butyl rubber matrix, selfreparing filler, toughening tension when preparation After stretching filler, vulcanization aid dispersion mixing, 127 DEG C of vulcanization 30min obtain self-repair type environment-protective rubber material.
Performance test
Tearing strength, tensile strength, impact rebound have been carried out to the rubber material of embodiment 1-4, comparative example 1-4 preparation The test of property, self-healing properties.Wherein, tearing strength, tensile strength, bounce impact elasticity respectively refer to standard GB/T529- 2008,GB/T528-2009,GB/T1681-1991.Self-healing properties be will stretch the rubber that cracks be placed on 50 DEG C it is flat On plate after 6h, tensile property is retested, tensile strength/initial tensile strength × 100% after self-healing properties=selfreparing, The bigger self-healing properties of numerical value are better.Specific test result is shown in Table 1.
1. rubber material the performance test results of table
As can be seen from the above table, the rubber material that the embodiment of the present invention is prepared, tearing strength, tensile strength, Comparative example is superior in bounce impact elasticity, self-healing properties.Tearing strength can achieve 26.5KN/m, and tensile strength can reach To 10.9MPa, bounce impact elasticity can achieve 62%, and self-healing properties reach 74.6%.Comparative example 1 is due to by selfreparing filler It has been substituted for selfreparing elastomeric prepolymer body in the prior art, a variety of interaction of hydrogen bond has been cannot achieve and resets reparation micro-meter scale Crack, cannot achieve good selfreparing effect so that bounce impact elasticity and self-healing properties reduce it is obvious.Comparative example 2 by In toughening stretch-proof filler is used nano silica, the filler of inorganic type is not easy in conjunction with rubber matrix, substantially reduces The tensile strength of rubber, toughness, elasticity modulus.
In the description of this specification, the description of reference term " one embodiment ", " example ", " specific example " etc. means Particular features, structures, materials, or characteristics described in conjunction with this embodiment or example are contained at least one implementation of the invention In example or example.In the present specification, schematic expression of the above terms may not refer to the same embodiment or example. Moreover, particular features, structures, materials, or characteristics described can be in any one or more of the embodiments or examples to close Suitable mode combines.
Above content is only citing made for the present invention and explanation, affiliated those skilled in the art are to being retouched The specific embodiment stated does various modifications or additions or is substituted in a similar manner, and without departing from invention or surpasses More range defined in the claims, is within the scope of protection of the invention.

Claims (5)

1. a kind of self-repair type environment-protective rubber material, which is characterized in that the ingredient including following parts by weight: butyl rubber matrix 80-100 parts, 22-30 parts of selfreparing filler, 15-26 parts of toughening stretch-proof filler, 6-13 parts of vulcanization aid dispersion；Wherein, sulphur Change auxiliary agent dispersion to be composed of the following components in parts by weight: 1-3 parts of zinc oxide, 4-6 parts of bentonite, sodium carboxymethylcellulose 0.2- 0.8 part, 0.6-1.2 parts of Vulcanization accelerator TMTD, 1.5-2.5 parts of expanded graphite；
The preparation method of the selfreparing filler the following steps are included:
1) polyether polyol 330N is mixed with double amino-terminated linear polydimethylsiloxane-s according to mass ratio 1:0.9-1.1 After even, 100-110 DEG C of vacuum defoamation handles to obtain mixed liquor a；Wherein, the hydroxyl value of polyether polyol 330N is 55-58mg KOH/ G, acid value≤0.15mg KOH/g, moisture content≤0.1%；The viscosity of double amino-terminated linear polydimethylsiloxane-s is 4500- 4600mPa·s；
2) isophorone diisocyanate and dibutyl tin dilaurate are added into mixed liquor a, is warming up to 65-75 DEG C and stirs 20-30min, then it is warming up to 100-110 DEG C of reaction 2-3h, it stands to room temperature and obtains performed polymer；Wherein, isophorone diisocyanate The additive amount of ester is the 5%-10% of polyether polyol 330N mass, and the additive amount of dibutyl tin dilaurate is polyether polyol The 0.5-3% of 330N mass；
3) performed polymer is dissolved in acetone and obtains prepolymer solution, use 3, the 3'- dihydroxy hexichol two of acetone solution in advance Thioether is slowly dropped in prepolymer solution, and after being added dropwise, 40-50 DEG C of stirring 40-60min pours into Teflon mould In, 60-70 DEG C of vacuum, which is crosslinked 12-16 hours, obtains selfreparing filler.
2. self-repair type environment-protective rubber material according to claim 1, which is characterized in that the toughening stretch-proof filler The preparation method is as follows: graphene oxide is uniformly mixed with mother-of-pearl dispersion liquid according to mass ratio 1:6-8, the shake of 100-200W ultrasound It swings 10-20min and obtains dispersion, Tris buffer solution is added by dispersion pH value and is adjusted to 8.5, pours into vacuum after mold It filters, 105-110 DEG C of vacuum drying is ground into the powdered of partial size 1-2mm at solid-like.
3. self-repair type environment-protective rubber material according to claim 2, which is characterized in that the system of the mother-of-pearl dispersion liquid Preparation Method is as follows: choosing pearl shell, cuts the salt acid soak 5-10min for using 20vt% after the impurity of surface layer, reuse clear water It rinses, the tablet of precomminution growth 1-2cm, width 1-2cm are put into ball mill, the ball under 35-45 DEG C, 300-400r/min Mill 2-3h obtains ball milling material, and 10-12 times of quality of ball milling material of deionized water, ultrasonic vibration 10-20min at 40-50 DEG C is added.
4. self-repair type environment-protective rubber material according to claim 2, which is characterized in that the preparation of the graphene oxide Method is as follows: 1.2g expanded graphite, 20mL water, the hydrogen peroxide of 5mL volumetric concentration 27.5%, 0.5g grass are sequentially added into beaker Acid is mixing uniformly to form slurry, and the slurry mixed sprays into 215-225 DEG C of gasification burner by booster pump with Sprayable In, slurry gasifies to form gas and absorb by tube-cooled, isolates solid powder, filters, and washing is dried to obtain；Wherein, The density of expanded graphite is 1.92-1.95g/cm3, crystal particle diameter is 50-60 mesh, and scale is having a size of 280-300 μm.
5. a kind of preparation method of self-repair type environment-protective rubber material, which comprises the following steps:
S1,1-3 parts of zinc oxide, 4-6 parts of bentonite, 0.2-0.8 parts of sodium carboxymethylcellulose, Vulcanization accelerator TMTD 0.6-1.2 are weighed Part, 1.5-2.5 part of expanded graphite, obtain mixture after mixing, in mixture addition ball mill, at 40-50 DEG C with Revolving speed ball milling 2-3 hours of 350-400r/min obtain vulcanization aid dispersion；
S2, butyl rubber matrix, selfreparing filler, toughening stretch-proof filler are put into rubber mixing mill, mixing 20-30min, It pours into Teflon mould, 90-100 DEG C obtains rubber semi-finished product in vacuumize process 1-2 hours；
S3, vulcanization aid dispersion is added in rubber semi-finished product, 120-130 DEG C of vulcanization 20-30min obtains the self-repair type Environment-protective rubber material.
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CN113880495A (en) * 2021-11-05 2022-01-04 禹智环保科技（深圳）有限公司 Natural color water-permeable adhesive stone pavement material and preparation process thereof

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